Hard resins



Patented Oct. 16, 1945 HARD RESINS Ferdinand P.

bury, N. J., assign York ors Company, Incorporate Otto and Orland M.Belfl', weed-- to Socony-Vacuum 011 d, a corporation of New No Drawing.Application September 15, 1943,

Serial No. 502,507

4 Claims.

This invention has reference to a resinous composition of matter and isparticularly concerned with a hard resin derived by mono-alkylation ofaromatic bodies. This application is a continuation-impart of ourcopending application Serial No. 423,580, filed December 19, 1941 nowPatent No. 2,340,838.

In one respect, the present invention is related to the disclosure ofPatent No. 2,191,498, issued February 27, 1940, to O. M. Bell! and thecopenddug application of 0. M. Reifl and J. ,J. Giammaria, Serial No.427,588, filed January 21, 1942. Both of said disclosures are directedto aromatic compounds and mixtures of aromatic compounds which have beensubstituted with long chain aliphatic radicals by a Friedel-Craftsreaction. In both instances, the aliphatic radical is preferably derivedfrom petroleum wax.-

In these respects the present disclosure resembles the earlierdisclosures noted above. As respects properties of the compositionsconcerned, the present invention relates to material of widely difierentnature. The products of the said patent are viscous liquids, soluble inlubricating oil, obtained by reaction of aromatics with chlorinated waxof about 14% chlorine content in such proportions as to polyallrylatethe aromatic. The compositions described in the said application areplastic, rubber-like masses insoluble in hydrocarbon OllS which resultfrom reaction of an excess of chlorinated wax of high chlorine content(more than 25%) with aromatic compounds.

The products of this invention are hard resinous bodies soluble invarnish resin solvents and are derived by reacting highly chlorinatedwax, orother suitable aliphatic hydrocarbons, containing from about 40%rine with aromatic compounds andmixtures of such compounds inproportions to theoretically result in mono-alkylation of the aromatic.Prererably, the aromatic reactant is used in substantial excess withrespect to the chlorine content. By following the teachings of thisinvention as outlined above and described in greater detail below, thedesired hard resin is obtained in a form admirably suited to theformation of fine coating compositions and for other purposes that willbe apparent to those skilled in the art.

01 the two reactants, the chlorinated aliphatic seems to be the 'moreimportant in afiecting the characteristics of the final product. Goodresults are obtained with general by reaction with having upwards oiabout aliphatic hydrocarbons carbon atoms, which toabout 60% of chic--aromatic compounds in p hydrocarbons have been chlorinated to the extentof about 40% to by weight. Preferably, an aliphatic compound of about50% chlorine content is employed. Some variations in properties of theresins are noted with variations in the character of the aromatic usedbut the general properties of a hard resin are found within the abovehmits of chlorination when the proportions of reactants are such thatthere is present in the reaction mixture at least one mol of aromaticcompound for each mol of combined chlorine in the chlorinated aliphatic.It is understood, of course, that other halogens than chlorine areavailable for the purposes of the invention and chlorine is discussedhere as exemplary because it is the halogen generally used for thepresent purpose.

Although aliphatic compounds and mixtures of relatively low molecularweight, about 10 carbon atoms, are suitable, best results are obtainedby the use of chlorinated petroleum waxes. Such waxes often contain somecomponents of as few as 15 carbon atoms but the predominant por-= tionof any such wax is usually composed of allphatic hydrocarbons of 20 ormore carbon atoms with an average of about 24 carbon atoms and anaverage molecular weight of about 350.

The hard, resin compositions derived from the reaction of chlorinatedwas with aromatic compounds, might be more aptly described as arylatedwaxes because of their high aromatic content. Hard resins derived fromphenol, 'for instance, have a combined phenol content of about 40%, theremainder of the molecule consisting of combined wax. A trace ofchlorine is ordinarily present from incomplete reaction, but is notnecessary for the formation of a hard resin.

.The compositions may be represented by the following general formulaewhich is not an attempt to give, however, an exact representation of themolecule. For simplicity, aromatic nuclei are represented by the phenylthe difierent Although a sufllcient amount oi! the aromatic compounds isused'in the reaction with the chlorinated wax that onlymono-substitution of the aromatic nucleus should occur theoretically. asrepresented by the first formula, apparently some poly-substitution alsotakes place as represented by the second formula. The compounds arerepresented with a single attachment of the arcmatic group to each waxgroup, but where polysubstitution occurs, apparently the aromatic groupwill be attached in some cases to more than one carbon of the same waxgroup, particularly in reactions with aromatic compounds of thecondensed nuclei and polycyclic type.

The foregoing conclusions are substantiated by the molecular weights ofthe wax aromatic resins which were determined by the boiling pointmethod, using benzene as solvent. The following results were obtained:

Some chain formation would be expected to occur in the reaction ofaromatic compounds with highly chlorinated waxes, in which case thefollowing representation would be applicable, but the low molecularweights of the resins indicate little chaining of the arylated waxmolecules.

QQQQQQ The resins consist apparently of a mixture of the compoundsrepresented by formula 1, 2 and '3. Because of the complexity of themixtures,

noattempt has been made to separate the resins into their constituents.

The difierent aromatic compounds are not equivalent in respect to thedegree of chlorination of the wax required to produce a resin of thesame degree of hardness and same melting point. Further. each aromaticcompound can be reacted with chlor-wax of variable chlorine content toobtain products of different degrees of hardness and different meltingpoints. For a chlorinated wax of different chlorine content, a harderresin is derived from phenol than from aromatic hydrocarbons or aromaticethers. In the following examples, a proportion of reactants is givenwhereby a resin of desirable degree of hardness and suitable meltingpoint can be formed from different aromatic compounds. Examples only ofunsubstituted hydroxyaromatic and aromatic hydrocarbons and aromaticethers are given. Aromatic compounds containing low molecular weightalkyl substituents as in the case of toluene, xylene andmethyl-naphthalene require reaction with chlorinated wax of higherchlorine content to obtain a resin of comparable hardness.

rinated wax at EXAMPLE I WAX Palmer. Rrsm Reaction mixture GramsChlorinated wax of 45% chlorine content 600' Phenol in excess of amountrequired 1 for reaction) 1430 A1013 (30% by weight, based on weight ofchlorinated wax) 180 Zinc dust (for decolorizing) 300 60 C. with rapidstirring. The temperature of r the mixture is gradually raised to about1'75 C. during a 2-hour period and held at this point until theevolution of HCl is complete, which will require about 4 hours.

The color of the reaction'mixture can be lightened by the reducingaction 01 zinc dust and dilute hydrochloric acid. This reduction iscarried out by adding 300 grams of zinc dust and 100 cc. of water atabout 90 C. and stirring the mixture several hours. In order to obtain aproduct of lighter color, it is desirable to add additional hydrochloricacid and continue the reduction several hours longer. As an aid tostirring the reaction mixture, it is desirable to add about 500 cc. ofbenzene before carrying out the reduction procedure. The reactionmixture is then filtered to remove excess zinc, followed by waterwashing to remove acid, zinc chloride and aluminum chloride and thentopping by heating to about 180 F. under diminished pressure to removesolvent and unreacted phenol. The product obtained is a light brown,hard resin of about 40% phenol content.

- This reaction procedure is applicable to the production of hard resinsfrom hydroxyaromatic compounds in general. In the preparation of hardresins by the reaction of chlorinated'wax with aromatic hydrocarbons andaromatic ethers, essentially the same reaction procedure is used. LessAlCls is required for the reaction. In the formation of hard resins fromthe following reaction mixtures, a top reaction temperature of about C.is used in carrying but the Friedel- Crafts reaction. In the case ofaromatic hydrocarbons boiling below 150 0., the Friedel-Crafts reactionis carried out at the boiling point of the aromatic compounds. Benzene,for instance, is converted to a hard resin by reaction with chlo- C.Reaction mixtures for several resins within the scope of the inventionare set out below.

EXAMPLE n Wax Bmznm: Rnsm Grams Chlorinated wax of 50% chlorine content-150 Benzene (100% in excess of amount required for reaction) 330 A101:(20% by weight based on chlorwax) 30 Zinc dust (for decolorizing) 100EXAMPLE III Wax mm Rrsm Grams Chlorinated wax of 50% chlorine content150 Diphenyl (50% in excess of amount required for reaction) 485 AlCla30 Zinc dust (for decolorizing) 100 EXAMPLEIV Wax Narnrmnm Rasm GramsChlorinated wax of 50% chlorine content 140 Naphthalene (100% in excessof amount required for reaction) 520 A101: 28 Zinc dust (fordecolorizing) 100 EXAMPLE v Wax, Drrnamoxmn Rnsm Grams Chlorinated waxof 50% chlorine content 100 Diphenyloxide (50% in excess of amountrequired for reaction 348 A101: 20 Zinc dust 100 EXAMPLEVI Rrsm rxomRnacrron or CHLORINATED Sronmmo SOLVENT WITH PHENOL Reaction mt'rtm'eGrams Chlorinated Stoddard solvent, 50% chlorine content 150 Phenol(100% in excess of amount required for reaction) 404 Aluminum chloride(30% basedon weight of chlorinated aliphatic) 45 Zinc dust.. 100

To a reaction mixture consisting of the chlorinated Stoddard solvent andphenol at 55 C. is added 45 grams of aluminum chloride. Thetemperature'is then gradually raised to 175 C. and

' held there until the evolution of hydrogen chloride practicallyceases, which will require about 2 hours. The reduction step thenfollows, consisting of dilution with 300 cc. of Stoddard solvent and theaddition of zinc dust and 30 cc. of water, followed by refluxing themixture for two hours. At this point, it is desirable to add 100 cc. ofconcentrated hydrochloric acid and continue the reduction'for severalhours .longer to obtain improved decolorization. The product is thenfiltered, water washed until neutral and topped to 200 C. underdiminished pressure (5 mm.) to

remove the excess phenol and solvent. The product obtained is adark-brown hard resin. The

resins prepared according to the foregoing examples are generally lightbrown in color but may be substantially improved as to color bycatalytic hydrogenation without materially aflecting their physicalproperties. Raney nickel is anexcellent catalyst for this purpose andthe color of the resins may be reduced to pale yellow by procedures setout below.

EXAMPLE VII Grams Wax diphenyl of ExampleIII Dioxane 500 Raney nickel 20The resin is dissolved in approximately five a high pressure shaker-bombalong with 20% by \weight of Raney nickel catalyst. The catalyst isprepared according to Covert and Adkins, J. A. C.'S. 54, 4116, (1932).The initial pressure of hydrogen in the bomb is 1500 lbs. per squareinch. The temperature is then raised to 500 F. and held there for aperiod of 7 hours during which time the pressure remains at 2700 lbs.per square inch. After cooling, the reaction mixture is removed from thebomb and filtered to remove catalyst. This is followed by topping to C.under diminished pressure (5 mm.) to remove the solvent and to obtainthe finished, Product.

LE VIII Grams Wax phenol of Example I 100 Dioxane 500 Raney nickel- '20The treatment is conducted in substantially the same fashion as inExample VII.

The alkylated aromatic compounds will undergo chemical reactions ofwhich the parent aromatic compounds are capable, but with formation ofproducts of different physical characteristics. The hard resins can beimproved, for instance, by reaction with formaldehyde and otherresinifying agents. 4

The hard resins vary from brown to pale yellow or colorless compoundsdepending upon the degree of reduction with hydrogen. The resins aresoluble in varnish resin solvents and have been found to give highlydesirable coatings.

Although the resin-forming reaction has been described as conducted withthe use of an aluminum chloride catalyst, it will be understood that anysuitable alkylation catalyst may be-used, preferably a catalyst of thetype employed in Friedel-Crafts reactions in general.

It will be seen that the invention is equally applicable to the use ofpure aromatic compounds and mixtures of aromatics, with or withoutcompounds other than aromatics, it being understood that proportionsrecited relate only to the reactive aromatic compounds and do notinclude diluents, impurities, and the like.

We claim:

1. A hard resinous light-colored composition of matter formed byreacting with the addition of heat diphenyl ether with a chlorinatedpetroleum wax containing about 40% to about 60% by weight of chlorine ina mol ratio of not less than one mol of said ether for each mol ofcombined chlorine in the presence of a Friedel-Crafts catalyst. addingmetallic zinc and water to reaction product to decolorize the same andcatalyticaily hydrogenating the product from treatment with zincformedby reacting with the addition of heat, di-

phenyl ether with a chlorinated petroleum wax containing about 40% toabout 60% by weight of chlorine in 9. mol ratio of not less than one moi0! said ether for each moi of combined chlorine in the presence of aFriedel-Crafts catalyst.

3. A hard resinous light-colored composition of matter formed byreacting with heat, diphenyl ether with a chlorinated petroleum waxcontaining about 50% by weight of chlorine in a moi ratio of not lessthan one mol of said ether for 01 a Friedel-Crafts catalyst, addingmetallic zinc and water to reaction product to decolorize the same andcatalyticaiiy hydrogenating the product from treatment with zinc andwater.

4. A hard resinous composition of matter formed by reacting diphenyiether with a chlorinated petroleum wax containing about 50% by weight ofchlorine in a moi ratio of not less than one mol 0! said ether for eachmoi of combined chlorine inthe presence of heat in the presence of aFriedel-Crafts catalyst.

FERDINAND P. OTTO: ORLAND M. REIF'F.

